Molasses binder

ABSTRACT

A binder based predominantly on molasses which incorporates both polymeric and monomeric polycarboxylic acid components to form a composite including both melanoidin and polyester polymeric structures. The binder incorporates the chemical profile of molasses with a mixture of polycarboxylic acids which combines to form a strong and weatherable binder composition which may be used to bind loosely or non-assembled matter.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority under 35 U.S.C. §119(e) to U.S.Provisional Patent Application No. 61/232,255, filed Aug. 7, 2009, thedisclosure of which is incorporated herein by reference in theirentirety.

TECHNICAL FIELD

This disclosure relates to a molasses binder composition for bindingloosely or non-assembled matter. In particular, a molasses bindercomposition and articles fabricated from binding non- or looselyassembled matter with a molasses binder composition is described.

BACKGROUND

Thermosetting binders comprise a variety of phenol-aldehyde,urea-aldehyde, melamine-aldehyde, and other condensation-polymerizationmaterials like the furane and polyurethane resins. Thermosetting bindersmay be characterized by being transformed into insoluble and infusiblematerials by means of either heat or catalytic action. Bindercompositions containing phenol-, resorcinol-, urea-,melamine-formaldehyde, phenolfurfuraldehyde, and the like are used forthe bonding of textiles, plastics, rubbers, and many other materials.

The effluent obtained in the preparation of sucrose by repeatedevaporation, crystallization and centrifugation of juices from sugarcane and from sugar beets is referred to as molasses. Cane molasses is aby-product of the manufacture or refining of sucrose from sugar cane.Beet molasses is a by-product of the manufacture of sucrose from sugarbeets. Citrus molasses is the partially dehydrated juices obtained fromthe manufacture of dried citrus pulp. Hemicellulose extract is a mixtureof pentose and hexose sugars which is a by-product of the manufacture ofpressed wood. Specifically hemicellulose extract is a molasses that isthe concentrated soluble material obtained from the treatment of wood atelevated temperature and pressure, typically without use of acids,alkalis, or salts. Starch molasses is a by-product of dextrosemanufactured from starch derived from corn or grain sorghums wherein thestarch is hydrolyzed by enzymes and/or acid.

Historically, molasses has been used as a binder within variouscommercial products. For example, U.S. Pat. No. 3,961,081 describesusing molasses as a binder in preparing livestock feed. U.S. Pat. No.5,416,139 describes using molasses as a binder in the manufacture ofstructural building materials and French Published Application FR2,924,719 describes using molasses in the manufacture of mineral woolinsulation materials.

The glass wool or mineral wool industry has historically used a phenolformaldehyde (PF) binder to bind the fibers. PF binders provide suitableproperties to the final products; however, environmental considerationshave motivated the development of alternative binders. One suchalternative binder is the nitrogenous polymer derived from reacting acarbohydrate and an amine base, for example, U.S. Published ApplicationNo. 2005/0027283. Another alternative binder is the esterificationproducts of reacting a polycarboxylic acid and a polyol, for example,U.S. Published Application No. 2005/0202224.

SUMMARY OF THE DISCLOSURE

According to the present disclosure, a binder composition comprisesmolasses and a polycarboxylic acid formulated for causing cohesion uponcontacting non- or loosely assembled matter.

In illustrative embodiments, the binder comprises molasses, a monomericpolycarboxylic acid and a polymeric polycarboxylic acid. In oneembodiment, the binder exhibits significant resistance to weathering. Inone embodiment, the binder is a composite melanoidin and polyesterproduct comprising products of reacting a molasses with a polymericpolycarboxylic acid and monomeric polycarboxylic acid in the presence ofa sodium hypophosphite catalyst. In another embodiment, the ratio of thepolymeric polycarboxylic acid to the monomeric polycarboxylic acid isfrom about 0.25 to about 1.5 by weight.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the shell bone longitudinal tensile strength test forweathered and dry samples for comparative example 1-4, examples 1-10 anda reference composition.

DETAILED DESCRIPTION

While the invention is susceptible to various modifications andalternative forms, specific embodiments will herein be described indetail. It should be understood, however, that there is no intent tolimit the invention to the particular forms described, but on thecontrary, the intention is to cover all modifications, equivalents, andalternatives falling within the spirit and scope of the invention.

It should be appreciated that the binders described herein may be usedin manufacturing products from a collection of non- or loosely assembledmatter. For example, these binders may be employed to fabricate fiberproducts. These products may be made from woven or non-woven fibers. Thefibers can be heat-resistant or non-heat-resistant fibers orcombinations thereof. In one illustrative embodiment, the binders areused to bind mineral fibers to make mineral wool thermal insulation. Forexample, the binders are used to bind glass fibers to make fiberglass.In another illustrative embodiment, the binders are used to makecellulosic compositions. With respect to cellulosic compositions, thebinders may be used to bind cellulosic matter to fabricate, for example,wood fiber board which has desirable physical properties (e.g.,mechanical strength).

One embodiment of the invention is directed to a method formanufacturing products from a collection of non- or loosely assembledmatter. One example of using this method is in the fabrication ofmineral wool insulation, for example fiberglass. Another example ofusing this method is the fabrication of rock wool thermal insulation.Yet another example of using this method is the fabrication of woodboard from cellulosic fibers. However, as indicated above, this methodcan be utilized in the fabrication of any material, as long as themethod produces or promotes cohesion when utilized.

As used herein, the phrase “formaldehyde-free” means that a binder or amaterial that incorporates a binder liberates less than about 1 ppmformaldehyde as a result of drying and/or curing. The 1 ppm is based onthe weight of sample being measured for formaldehyde release. One aspectof the present invention is that the binders described herein can bemanufactured as formaldehyde-free.

The term “cured” indicates that the binder has been exposed toconditions so as to initiate a chemical change. Examples of thesechemical changes include, but are not limited to, (i) covalent bonding,(ii) hydrogen bonding of binder components, and chemically cross-linkingthe polymers and/or oligomers in the binder. These changes may increasethe binder's durability and solvent resistance as compared to theuncured binder. Curing a binder may result in the formation of athermoset material. In addition, a cured binder may result in anincrease in adhesion between the matter in a collection as compared toan uncured binder. Curing can be initiated by, for example, heat,electromagnetic radiation or, electron beams.

In a situation where the chemical change in the binder results in therelease of water, e.g. polymerization and cross-linking, a cure can bedetermined by the amount of water released above that would occur fromdrying alone. The techniques used to measure the amount of waterreleased during drying as compared to when a binder is cured, are wellknown in the art. In contrast, an uncured binder is one that has notbeen cured.

In illustrative embodiments, a binder composition comprises a polymericproduct of a reaction between molasses, a polymeric polycarboxylic acid,and a monomeric polycarboxylic acid. In one embodiment, the polymericproduct comprises predominantly molasses. For example the polymericproduct has a total weight that is attributable primarily to the amountof molasses used or the weight percentage of molasses is greater thanthe weight percentage of all other components. In another embodiment,the binder composition is a polymeric product of a catalyzed reactionbetween molasses, a polymeric polycarboxylic acid, and a monomericpolycarboxylic acid. For example, sodium hypophosphite may be used as acatalyst.

As used herein, molasses is a by-product of the manufacture of purifiedsugars or the soluble material obtained from the treatment of wood. Forexample, the final effluent obtained in the preparation of sucrose byrepeated evaporation, crystallization and centrifugation of juices fromsugar cane and from sugar beets is referred to as molasses. During themanufacture of the sucrose, crystallization is used to remove sucrosefrom a super-saturated solution. After crystallization, the solutionleft behind includes a complex mixture of compounds which varies incomposition according to plant source, location grown, season, age, andweather conditions. Furthermore, the efficiency and steps taken tocrystallize the sucrose can result in compositional variation betweenmolasses. For example, with the improvement of continuous centrifugationmethods, the extraction of crystallized sucrose has become moreefficient, therefore, modern molasses contains relatively less sucrose.

Examples of molasses include cane molasses, which is a by-product of themanufacture or refining of sucrose from sugar cane. Beet molasses is aby-product of the manufacture of sucrose from sugar beets. Citrusmolasses is the partially dehydrated juices obtained from themanufacture of dried citrus pulp. Hemicellulose extract is a mixture ofpentose and hexose sugars which is a by-product of the manufacture ofpressed wood. Specifically hemicellulose extract is a molasses that isthe concentrated soluble material obtained from the treatment of wood atelevated temperature and pressure without use of acids, alkalis, orsalts. Starch molasses is a by-product of dextrose manufactured fromstarch derived from corn or grain sorghums wherein the starch ishydrolyzed by enzymes and/or acid.

A representative molasses is a liquid being approximately 25% water byweight. Molasses may be diluted or evaporated to adjust the weightpercent of water; however, as used herein, the weight percentages arebased on a molasses that includes 25% by weight water. Molasses ischaracterized as having a high concentration of sugars; for example,molasses may have total sugars of about 50% by weight. Thisconcentration may vary significantly; concentrations of total sugars inmolasses may vary from about 30-60% by weight. The density of molassesranges from about 1.3 to about 1.5 g/mL and organic matter comprisesabout 55-70%. Nitrogen content may vary from about 0.5-3% as determinedby elemental analysis. The nitrogen content is in the form of proteins,amino acids, and oligomers thereof. Protein may comprise about 5-10% ofthe total weight. The ratio of C:N as determined by elemental analysismay be in the range from about 50:1 to about 15:1.

The sugar content is primarily a mixture of sucrose, dextrose, andfructose. The mixture also contains a number of vitamins and mineralswhich remain soluble during the crystallization of the sucrose. Forexample, elemental analysis shows that molasses is a source of calcium,potassium, chloride, magnesium, sulfur, sodium, copper, iron, manganese,and zinc. Other amino acids and vitamins found within molasses includebiotin, folic acid, inositol calcium pantothenate, pyridoxine,riboflavin, thiamine, niacin, and choline. Molasses may act as a bufferwith a pH in the range of about 4 to about 7.

In illustrative embodiments, a binder composition comprises a molasseshaving a carbon to nitrogen ratio of less about 27:1 as determined byelemental analysis. While not being limited to theory, it is believedthat the nitrogen content of molasses is in the form of proteins andamino acids which are capable of reacting with the reducing sugarswithin molasses to form melanoidin products. Melanoidin products arenitrogenous polymers or oligomers which are characteristically brown incolor. It is believed that molasses obtains its naturally brown color,at least in part, from the formation of these products. These melanoidinproducts are capable of further reaction under the appropriateconditions. For example, in the presence of carboxylic acids, esterlinkages may form between 1 or more molecules of a polycarboxylic acidand one or more molecules of a melanoidin product. The concentration ofthe melanoidin products is believed to initially be quite low. Withoutdehydration, catalysis, or being subjected to curative temperatures,molasses is known to be a stable composition that does not exhibitsubstantial changes over time.

In illustrative embodiments, molasses comprising less than about 70%sugar by dry weight may be used to form the binder composition of thepresent disclosure. In one embodiment, the binder comprises a molassesincluding about 3% to about 16% reducing sugar by weight. In anotherembodiment, the molasses can be derived from sugar cane. In alternativeembodiments, the molasses may be derived from alternative sources suchas sugar beets, corn, maize, citrus fruits or wood products. Accordingto one aspect of the present disclosure, the selection of molasses typemay influence the relative ratio of the polymeric and monomericpolycarboxylic acids which may be used to produce a binder.

In illustrative embodiments, the binder composition is predominantlycomprised of molasses. In one embodiment, the ratio of the molasses to acombination of the molasses, the polymeric polycarboxylic acid, and themonomeric polycarboxylic acid is from about 0.5 to about 0.9 by weight.In another embodiment, the ratio of the molasses to the combination ofthe molasses, the polymeric polycarboxylic acid, and the monomericpolycarboxylic acid is from about 0.6 to about 0.8 by weight.

In illustrative embodiments, molasses may be partially or completelysubstituted by dextrin. Dextrin is a term used to describe the group oflow-molecular-weight carbohydrates produced by the hydrolysis of starch.Dextrins are mixtures of linear α-(1,4)-linked D-glucose polymersstarting with an α-(1,6) bond. In one embodiment, the dextrin comprisesmaltodextrin. The method of producing the dextrin may have a substantialaffect on its chemical composition, however, these methods arewell-known in the art. In illustrative embodiments, the dextrin isderived from flora-derived starch. In one embodiment, the flora is atuber such as a potato, cassava, arrowroot, yam, or sweet potato. Inanother embodiment, the flora is a seed such as corn, corn, rye, rice,barley, millet, oats or sorghum. In yet another embodiment, the flora isa nut such as chestnut, sweet chestnut, or hazel nut. In yet anotherembodiment the flora is a vegetable as peas or bean.

In illustrative embodiments, the dextrin has a dextrose equivalent ofabout 5 to about 100. In one embodiment, the dextrin has a dextroseequivalent of about 10 to about 75. In another embodiment, the dextrinhas a dextrose equivalent of about 15 to about 50.

One aspect of the present disclosure is that molasses is a renewablefeed-stock. As such, the materials bound with a binder of the presentdisclosure may be manufactured using a predominantly bio-based renewablefeed-stock. Accordingly, the binder is predominantly bio-based and isthus not predominantly petroleum-based.

In illustrative embodiments, the binder composition comprises apolymeric polycarboxylic acid. As used herein, a polymericpolycarboxylic acid is an organic polymer or oligomer containing morethan five pendant carboxy group. A polymeric polycarboxylic acid may bea homopolymer or copolymer prepared from unsaturated carboxylic acidsincluding, but not necessarily limited to, acrylic acid, methacrylicacid, crotonic acid, isocrotonic acid, maleic acid, cinnamic acid,2-methylmaleic acid, itaconic acid, 2-methylitaconic acid,α,β-methyleneglutamic acid, and the like. Alternatively, the polymericpolycarboxylic acid may be prepared from unsaturated anhydridesincluding, but not necessarily limited to, maleic anhydride, itaconicanhydride, acrylic anhydride, methacrylic anhydride, and the like, aswell as mixtures thereof. Methods for polymerizing these acids andanhydrides are well-known in the chemical art. The polymericpolycarboxylic acid may additionally comprise a copolymer of one or moreof the aforementioned unsaturated carboxylic acids or anhydrides and oneor more vinyl compounds including, but not necessarily limited to,styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, methylacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methylmethacrylate, n-butyl methacrylate, isobutyl methacrylate, glycidylmethacrylate, vinyl methyl ether, vinyl acetate, and the like. Methodsfor preparing these copolymers are well-known in the art. Inillustrative embodiments, the polymeric polycarboxylic acid compriseshomopolymers and copolymers of polyacrylic acid. In another embodiment,the polymeric polycarboxylic acid comprises homopolymers and copolymersof maleic anhydride.

In illustrative embodiments, the polymeric polycarboxylic acid is a lowmolecular weight polymer. As used herein, the term low molecular weightpolymer includes those polymers having a molecular weight of less thanabout 10,000 g/mol. In one embodiment, the polymeric polycarboxylic acidhas a molecular weight of from about 1000 to about 8000 g/mol. Inanother embodiment, the polymeric polycarboxylic acid has a molecularweight from about 2000 to about 5000 g/mol. One aspect of the presentdisclosure is that the molecular weight of the polymeric polycarboxylicacid may affect the weatherability of the resulting binder. The utilityof higher molecular weight polymeric polycarboxylic acids may be limitedby solubility, viscosity, or structural limitations.

Illustratively, a polymeric polycarboxylic acid may be an acid, forexample, polyacrylic acid, polymethacrylic acid, polymaleic acid, andlike polymeric polycarboxylic acids, copolymers thereof, anhydridesthereof, and mixtures thereof. Examples of commercially availablepolyacrylic acids include AQUASET-529 (Rohm & Haas, Philadelphia, Pa.,USA), CRITERION 2000 (Kemira, Helsinki, Finland, Europe), NF1 (H.B.Fuller, St. Paul, Minn., USA), and SOKALAN (BASF, Ludwigshafen, Germany,Europe). With respect to SOKALAN, this is a water-soluble polyacrylicpolymer or copolymer. Grades of SOKALAN include homopolymers of acrylicacid and various copolymers. For example, one grade is a homopolymer ofacrylic acid having a molecular weight of approximately 4000 g/mol.Another example is a copolymer of acrylic acid and maleic acid having amolecular weight of approximately 4000 g/mol. AQUASET-529 is acomposition containing polyacrylic acid cross-linked with glycerol, alsocontaining sodium hypophosphite as a catalyst. CRITERION 2000 is anacidic solution of a partial salt of polyacrylic acid, having amolecular weight of approximately 2000 g/mol. With respect to NF1, thisis a copolymer containing carboxylic acid functionality and hydroxyfunctionality, as well as units with neither functionality; NF1 alsocontains chain transfer agents, such as sodium hypophosphite ororganophosphate catalysts.

In one embodiment, the binder composition comprises a polymericpolycarboxylic acid. In one embodiment, the binder composition comprisesa polymeric polyacrylic acid. In another embodiment, the bindercomposition comprises a copolymer of an acrylic acid and a maleicanhydride. In another embodiment, the binder composition comprises apolymeric polycarboxylic acid having a molecular weight of about 2000 toabout 6000 g/mol.

In illustrative embodiments, the binder composition comprises amonomeric polycarboxylic acid. As used herein, the term “polycarboxylicacid” indicates a dicarboxylic, tricarboxylic, tetracarboxylic,pentacarboxylic, and like monomeric polycarboxylic acids, andanhydrides, and combinations thereof. Illustratively, a monomericpolycarboxylic acid may be a dicarboxylic acid, including, but notlimited to, unsaturated aliphatic dicarboxylic acids, saturatedaliphatic dicarboxylic acids, aromatic dicarboxylic acids, unsaturatedcyclic dicarboxylic acids, saturated cyclic dicarboxylic acids,hydroxy-substituted derivatives thereof, and the like.

Illustratively, the polycarboxylic acid(s) itself may be a tricarboxylicacid, including, but not limited to, unsaturated aliphatic tricarboxylicacids, saturated aliphatic tricarboxylic acids, aromatic tricarboxylicacids, unsaturated cyclic tricarboxylic acids, saturated cyclictricarboxylic acids, hydroxy-substituted derivatives thereof, and thelike. It is appreciated that any such polycarboxylic acids may beoptionally substituted, such as with hydroxy, halo, alkyl, alkoxy, andthe like.

In one embodiment, the polycarboxylic acid is the saturated aliphatictricarboxylic acid, citric acid. In another, the polycarboxylic acids isaconitic acid, adipic acid, azelaic acid, butane tetracarboxylic aciddihydride, butane tricarboxylic acid, chlorendic acid, citraconic acid,dicyclopentadiene-maleic acid adducts, diethylenetriamine pentaaceticacid, adducts of dipentene and maleic acid, ethylenediamine tetraaceticacid (EDTA), fumaric acid, glutaric acid, isophthalic acid, itaconicacid, maleic acid, malic acid, mesaconic acid, biphenol A or bisphenol Freacted via the KOLBE-Schmidt reaction with carbon dioxide to introduce3-4 carboxyl groups, oxalic acid, phthalic acid, sebacic acid, succinicacid, tartaric acid, terephthalic acid, tetrabromophthalic acid,tetrachlorophthalic acid, tetrahydrophthalic acid, trimellitic acid,trimesic acid, or the like, or anhydrides, or combinations thereof. Inanother embodiment, the monomeric polycarboxylic acid is a mixture ofcitric acid and maleic acid or maleic anhydride.

One aspect of the present disclosure is that the monomericpolycarboxylic acid and the polymeric polycarboxylic acid work in asynergistic manner as crosslinking agents for constituents of themolasses as described herein. When exposed to curative temperatures, themonomeric polycarboxylic acid and the polymeric polycarboxylic acid arecapable of forming ester linkages between the various constituents ofthe molasses. Furthermore, as described herein, the monomericpolycarboxylic acid and the polymeric polycarboxylic acids facilitatethe reaction which results in the formation of additional melanoidinproducts. Additionally, the monomeric and polymeric polycarboxylic acidmay crosslink polyesters and/or polymeric melanoidins. In illustrativeembodiments, the catalyst facilitates esterification reactions withinthe scope of the foregoing reactions. Additionally, the polycarboxylicacid may serve in a catalytic role in the esterification and theMaillard reactions. The result of the melanoidin forming reactions andthe polyester forming reactions is a polymeric network which has ahighly cross-linked polymer network of substantial complexity withsurprisingly beneficial properties as a binder.

Another aspect of the present disclosure is that the combination of themonomeric polycarboxylic acid and the polymeric polycarboxylic acidovercomes limitations observed when either of a monomeric polycarboxylicacid or a polymeric polycarboxylic acid was used individually as acrosslinking agent. Specifically, it was observed that when a monomericpolycarboxylic acid was used without the addition of a polymericpolycarboxylic acid, the weatherability of the binder was insufficientfor many applications. Furthermore, binders comprising a polymericpolycarboxylic acid to the exclusion of a monomeric polycarboxylic acidyielded binders with sufficient strength and weatherability, but hadother adverse properties. For example, the viscosity of the reactivebinder solution was comparatively high, the cure times were relativelylonger, and the expense of the composition was relatively larger.

While not being limited to theory, it is believed that the advantage inmixing the monomeric and the polymeric polycarboxylic acid stems in partto the difference in physical and chemical properties that distinguishthese materials. Particularly, the differences in properties observed ina substantially dehydrated state. For example, the pKa of a monomericpolycarboxylic acid will be relatively lower than that of acorresponding polycarboxylic acid due to the effect of chargedelocalization along the polymeric backbone. Accordingly, the monomericpolycarboxylic acid will have a relatively larger influence on the acidcatalysis of the esterification than the polymeric polycarboxylic aciddue to its comparatively greater acidity. Furthermore, the monomericpolycarboxylic acid is capable of more complete homogenizationthroughout the dried uncured reaction mixture compared to the relativelylarger polymeric polycarboxylic acid.

For example, a polymeric chain may contain several hundred carboxylicacid groups in relatively close proximity. Accordingly, in asubstantially dried state, pockets which contain very high localconcentrations of strictly carboxylic acid functionality to theexclusion of melanoidin or sugar molecules may exist if the polymericpolycarboxylic acid was used alone. However, the small molecular weightof the monomeric polycarboxylic acid lowers the probability (i.e., it isentropically unfavorable) that a high concentration of carboxylic acidfunctionalities are in close proximity. Thus, the inclusion of themonomeric polycarboxylic acid provides the dried binder with arelatively higher degree of homogeneity for the dispersion of carboxylicacid functionality. In another aspect, the increased homogenization mayimprove availability of the reactive carboxylic acid groups to themolasses constituents. Another aspect is that the relatively smallmolecular cross-section of the monomeric polycarboxylic acid improvesits diffusion capabilities in a substantially dry reactive mixture.Again, this aspect would positively contribute to the availability ofthe carboxylic acid functionality to participate in esterifications.

One aspect in which the polymeric polycarboxylic acid contributes to thesynergistic relationship is that it possesses a relatively higher numberof carboxylic acid groups which are capable of crosslinking morecompounds through esterification. This facilitates the quick formationof relatively large polymeric units, thus increasing physicalperformance of the binder, such as tensile strength. Furthermore, thecross-linked molecular backbones will have as their backbones thecarbon-carbon bonds associated with the polymeric polycarboxylic acid asopposed to the esters. It is hypothesized that the presence of morecarbon-carbon bonds within the binder contributes to the improvedweatherability of this binder composition. It may be that theseattributes, at least in part, provide for the unexpected synergismbetween the monomeric polycarboxylic acid and the polymericpolycarboxylic acid within the scope of the present disclosure.

In illustrative embodiments, the monomeric polycarboxylic acid and thepolymeric polycarboxylic acid are added in substantially equivalentweights, the combination being as much as 50% of the total weight of thebinder. In one embodiment, the ratio of the monomeric polycarboxylicacid to the combination of the molasses, the polymeric polycarboxylicacid, and the monomeric polycarboxylic acid is from about 0.05 to about0.4 by weight. In another embodiment, the ratio of the monomericpolycarboxylic acid to the combination of the molasses, the polymericpolycarboxylic acid, and the monomeric polycarboxylic acid is from about0.1 to about 0.3 by weight. In another embodiment, the ratio of thepolymeric polycarboxylic acid to the combination of the molasses, thepolymeric polycarboxylic acid, and the monomeric polycarboxylic acid isfrom about 0.01 to about 0.4 by weight. In another embodiment, the ratioof the polymeric polycarboxylic acid to the combination of the molasses,the polymeric polycarboxylic acid, and the monomeric polycarboxylic acidis from about 0.03 to about 0.2 by weight. In another embodiment, theratio of the polymeric polycarboxylic acid to the monomericpolycarboxylic acid is from about 0.25 to about 1.5 by weight. In yetanother embodiment, the ratio of the polymeric polycarboxylic acid tothe monomeric polycarboxylic acid is from about 0.5 to about 1 byweight.

In illustrative embodiments, the binder composition may include acatalyst. For example, the catalyst may be an alkali metalpolyphosphate, an alkali metal dihydrogen phosphate, a polyphosphoricacid, and an alkyl phosphinic acid, an oligomer, a polymer bearingphosphorous-containing groups and mixtures thereof. Illustratively, thecatalyst may be sodium hypophosphite, sodium phosphite, potassiumphosphite, disodium pyrophosphate, tetrasodium pyrophosphate, sodiumtripolyphosphate, sodium hexametaphosphate, potassium phosphate,potassium polymetaphosphate, potassium polyphosphate, potassiumtripolyphosphate, sodium trimetaphosphate, or sodium tetrametaphosphate,or mixtures thereof. In one embodiment, the catalyst is sodiumhypophosphite. In one embodiment, the ratio of the catalyst to acombination of the molasses, the polymeric polycarboxylic acid, and themonomeric polycarboxylic acid is from about 0.001 to about 0.1 byweight. In another embodiment, the ratio of the catalyst to acombination of the molasses, the polymeric polycarboxylic acid, and themonomeric polycarboxylic acid is from about 0.003 to about 0.008 byweight.

As discussed below, various additives can be incorporated into thebinder composition. These additives give the binders of the presentinvention additional desirable characteristics. For example, the bindermay include a silicon-containing coupling agent. Many silicon-containingcoupling agents are commercially available from various manufacturers.For example, Dow-Corning Corporation, Petrarch Systems, AkzoNobel and bythe General Electric Company. Illustratively, the silicon-containingcoupling agent includes compounds such as silylethers and alkylsilylethers, each of which may be optionally substituted, such as withhalogen, alkoxy, amino, and the like. In one variation, thesilicon-containing compound is an amino-substituted silane, such as,gamma-aminopropyltriethoxy silane (General Electric Silicones, SILQUESTA-1101; Wilton, Conn.; USA). In another variation, thesilicon-containing compound is an amino-substituted silane, for example,aminoethylaminopropyltrimethoxy silane (Dow Z-6020; Dow Chemical,Midland, Mich.; USA). In another variation, the silicon-containingcompound is gamma-glycidoxypropyltrimethoxysilane (General ElectricSilicones, SILQUEST A-187). In yet another variation, thesilicon-containing compound is an n-propylamine silane (Creanova(formerly Huls America) HYDROSIL 2627; Creanova; Somerset, N.J.;U.S.A.).

The silicon-containing coupling agents are typically present in thebinder in the range from about 0.1 percent to about 1 percent by weightbased upon the dissolved binder solids (i.e., about 0.1 percent to about1 percent based upon the weight of the solids added to the aqueoussolution). In one application, one or more of these silicon-containingcompounds can be added to the aqueous uncured binder. The binder is thenapplied to the material to be bound. Thereafter, the binder may be curedif desired. These silicone containing compounds enhance the ability ofthe binder to adhere to the matter the binder is disposed on, such asglass fibers. Enhancing the binder's ability to adhere to the matterimproves, for example, its ability to produce or promote cohesion innon- or loosely assembled substance(s).

In another illustrative embodiment, a binder of the present inventionmay include one or more corrosion inhibitors. These corrosion inhibitorsprevent or inhibit the eating or wearing away of a substance, such as,metal caused by chemical decomposition brought about by an acid. When acorrosion inhibitor is included in a binder of the present invention,the binder's corrosivity is decreased as compared to the corrosivity ofthe binder without the inhibitor present. In one embodiment, thesecorrosion inhibitors can be utilized to decrease the corrosivity of thebinder-containing compositions described herein. Illustratively,corrosion inhibitors include one or more of the following, a dedustingoil, a monoammonium phosphate, sodium metasilicate pentahydrate,melamine, tin (II) oxalate, and/or methylhydrogen silicone fluidemulsion. When included in a binder of the present invention, corrosioninhibitors are typically present in the binder in the range from about0.5 percent to about 2 percent by weight based upon the dissolved bindersolids.

As described herein, binders can be used to produce or promote cohesionin non- or loosely assembled matter by placing the binder in contactwith the matter to be bound. Any number of well known techniques can beemployed to place the aqueous binder in contact with the material to bebound. For example, the aqueous binder can be sprayed on (for exampleduring the binding of glass fibers) or applied via a roll-coatapparatus.

For example, these binders can be applied to a mat of mineral fibers(e.g., sprayed onto the mat), during production of mineral woolinsulation products. Once the binder is in contact with the mineralfibers the residual heat from the mineral fibers (note that the mineralfibers are made from molten material and thus contain residual heat) andthe flow of air through the fibrous mat will evaporate (i.e., remove)water from the binder. Removing the water leaves the remainingcomponents of the binder on the fibers as a coating of viscous orsemi-viscous high-solids liquid. Further heating of the binder mayresult in a substantially dry uncured reactive mixture. This coating ofviscous, semi-viscous high-solids liquid or substantially dry binderfunctions as a binder. At this point, the mat has not been cured. Inother words, the uncured binder functions to bind the mineral fibers inthe mat.

Furthermore, it should be understood that the above described binderscan be cured. For example, any of the above described binders can bedisposed (e.g., sprayed) on the material to be bound, and then heated.For example, in the case of making mineral wool insulation products,after the aqueous binder has been applied to the mat, the binder coatedmat is transferred to a curing oven. In the curing oven the mat isheated (e.g., from about 150° C. [˜300° F.] to about 315° C. [˜600° F.])and the binder cures. The cured binder is a formaldehyde-free,water-resistant thermoset binder that attaches the mineral fibers of themat together. Note that the drying and thermal curing may occur eithersequentially, contemporaneously, or concurrently.

In illustrative embodiments, a method of binding loosely ornon-assembled matter includes the steps of mixing a solution comprisinga molasses, a monomeric polycarboxylic acid, a polymeric polycarboxylicacid, and a catalyst, disposing the solution on a collection of matter,and drying the solution to form a dehydrated reactive mixture. Themethod results in dehydrated reactive mixture binding the collection ofmatter. Illustratively, the composition as disclosed herein hasproperties that make it suitable for binding loosely or non-assembledmatter as an uncured material. While the uncured binder may be suitablefor temporary situations, it is expected that the binder will be cured.In one embodiment, the method of binding loosely or non-assembled matterincludes curing the dehydrated reactive mixture. In one embodiment, thecuring step includes heating the dehydrated reactive mixture totemperatures of from about 150° C. [˜300° F.] to about 315° C. [˜600°F.]. Illustratively, the curing step includes heating the dehydratedreactive mixture to about 175° C. [˜350° F.]. Illustratively, theloosely or non-assembled matter may comprise a collection of mineralfibers (e.g., glass, rock wool). In illustrative embodiments, the methodof binding loosely or non-assembled matter results in a binder which hasa shell bone longitudinal tensile strength test result average for aweathered and a dry sample exceeds about 1.8 MN/m² and 2.3 MN/m²respectively.

In illustrative embodiments, a composite melanoidin and polyester bindercomprises products of multiple reactions. First, melanoidin products mayform as the result of the reaction between the nitrogenous components ofthe molasses and the carbohydrate components of the molasses. Thisreaction may be catalyzed by and incorporate portions of the monomericpolycarboxylic acid. The melanoidins which form will have pendanthydroxyl groups derived from the carbohydrate and may undergoesterification reactions with other melanoidin products, with thepolymeric polycarboxylic acid, and/or with the monomeric polycarboxylicacid. This reaction may be catalyzed by an alkali metal polyphosphate.Additionally, the carbohydrate portion of the molasses may undergo anesterification reaction with either the monomeric or polymericpolycarboxylic acid catalyzed by the alkali metal polyphosphate.

For example, amine functional compounds from the molasses may react withreducing sugars from the molasses under influence of citric acid to formmelanoidin products. Furthermore, the melanoidin products may becross-linked by an esterification reaction with the polyacrylic acidand/or a citric acid under catalysis from sodium hypophosphite.Concurrently, a reaction between sugars in the molasses and thepolyacrylic acid and/or citric acid could also occur under catalysis ofsodium hypophosphite. In one embodiment, the ratio of the copolymer ofpolymeric polyacrylic acid to the monomeric polycarboxylic acid is fromabout 0.25 to about 1.5 by weight. In another embodiment, the polymericpolyacrylic acid has a molecular weight of about 2000 to about 6000g/mol. In yet another embodiment, the binder includes less than about 2%Nitrogen as determined by elemental analysis. In one embodiment, thesolution of the molasses with the polymeric polyacrylic acid and themonomeric polycarboxylic acid in the presence of the sodiumhypophosphite catalyst has a pH from about 6 to about 11. In yet anotherembodiment, an aqueous extraction of the binder has a pH from about 3 toabout 7.

Testing Procedures

When evaluated for their dry and weathered tensile strength, glassbead-containing shell bone compositions prepared with a given binderprovide an indication of the likely tensile strength and the likelydurability, respectively, of fiberglass insulation prepared with thatparticular binder. Predicted durability is based on a shell bone'sweathered tensile strength:dry tensile strength ratio. Shell bones wereprepared, weathered, and tested as follows:

Preparation Procedure for Shell Bones: A shell bone mold (DietertFoundry Testing Equipment; Heated Shell Curing Accessory, Model 366, andShell Mold Accessory) was set to a desired temperature, generally 200°C. [˜390° F.], and allowed to heat up for at least one hour. While theshell bone mold was heating, 60 g of an aqueous ammoniumpolycarboxylate-molasses binder (30% in binder solids) was prepared asdescribed in the examples set forth herein. Using a large glass beaker,582.0 g of glass beads (Quality Ballotini Impact Beads, Spec. AD, USSieve 70-140, 106-212 micron-#7, from Potters Industries, Inc.) wereweighed by difference. The glass beads were poured into a clean and drymixing bowl, which bowl was mounted onto an electric mixer stand.Exactly 60 g of aqueous binder were obtained, and the binder then pouredslowly into the glass beads in the mixing bowl. The electric mixer wasthen turned on and the glass beads/ammonium polycarboxylate-sugar bindermixture was agitated for one minute. Using a large spatula, the sides ofthe whisk (mixer) were scraped to remove any clumps of binder, whilealso scraping the edges wherein the glass beads lay in the bottom of thebowl. The mixer was then turned back on for an additional minute, thenthe whisk (mixer) was removed from the unit, followed by removal of themixing bowl containing the glass beads/binder mixture. Using a largespatula, as much of the binder and glass beads attached to the whisk(mixer) as possible were removed and then stirred into the glassbeads/binder mixture in the mixing bowl. The sides of the bowl were thenscraped to mix in any excess binder that might have accumulated on thesides. At this point, the glass beads/binder mixture was ready formolding in a shell bone mold.

The slides of the shell bone mold were confirmed to be aligned withinthe bottom mold platen. Using a large spatula, a glass beads/bindermixture was then quickly added into the three mold cavities within theshell bone mold. The surface of the mixture in each cavity was flattenedout, while scraping off the excess mixture to give a uniform surfacearea to the shell bone. Any inconsistencies or gaps that existed in anyof the cavities were filled in with additional glass beads/ammoniumpolycarboxylate-sugar binder mixture and then flattened out. Once aglass beads/binder mixture was placed into the shell bone cavities, andthe mixture was exposed to heat, curing began. As manipulation time canaffect test results, e.g., shell bones with two differentially curedlayers can be produced, shell bones were prepared consistently andrapidly. With the shell bone mold filled, the top platen was quicklyplaced onto the bottom platen. At the same time, or quickly thereafter,measurement of curing time was initiated by means of a stopwatch, duringwhich curing the temperature of the bottom platen ranged from about 160°C. [˜320° F.] to about 180° C. [˜355° F.], while the temperature of thetop platen ranged from about 200° C. [˜390° F.] to about 230° C. [˜445°F.]. At seven minutes elapsed time, the top platen was removed and theslides pulled out so that all three shell bones could be removed. Thefreshly made shell bones were then placed on a wire rack, adjacent tothe shell bone mold platen, and allowed to cool to room temperature.Thereafter, each shell bone was labeled, half were placed in adessicator and the other half in a humidity cabinet at 55° C. [˜130°F.]. All shell bones were tested the day after they were prepared.

Conditioning (Weathering) Procedure for Shell Bones: A Blue M humiditychamber was turned on and then set to provide weathering conditions of55° C. [˜130° F.] and 95% relative humidity (i.e., 55° C./95% rH). Thewater tank on the side of the humidity chamber was checked and filledregularly, usually each time it was turned on. The humidity chamber wasallowed to reach the specified weathering conditions over a period of atleast 4 hours, with a day-long equilibration period being typical. Shellbones to be weathered were loaded quickly (since while the doors areopen both the humidity and the temperature decrease), one at a timethrough the open humidity chamber doors, onto the upper, slotted shelfof the humidity chamber. The time that the shell bones were placed inthe humidity chamber was noted, and weathering conducted for a period of12 hours. Thereafter, the humidity chamber doors were opened and one setof shell bones at a time were removed and placed individually on a wirerack and left to cool. Weathered shell bones were immediately taken tothe Instron room and tested.

Test Procedure for Breaking Shell Bones: In the Instron room, the shellbone test method was loaded on the 5500 R Instron machine while ensuringthat the proper load cell was installed (i.e., Static Load Cell 1 kN),and the machine allowed to warm up for fifteen minutes. During thisperiod of time, shell bone testing grips were verified as beinginstalled on the machine. The load cell was zeroed and balanced, andthen one set of shell bones was tested at a time as follows: A shellbone was removed from its plastic storage bag and then weighed. Theweight (in grams) was then entered into the computer associated with theInstron machine. The measured thickness of the shell bone (in inches)was then entered, as specimen thickness, three times into the computerassociated with the Instron machine. A shell bone specimen was thenplaced into the grips on the Instron machine, and testing initiated viathe keypad on the Instron machine. After removing a shell bone specimen,the measured breaking point was entered into the computer associatedwith the Instron machine, and testing continued until all shell bones ina set were tested.

Referring now to FIG. 1, shown are the shell bone longitudinal tensilestrength test results for comparative samples 1-2, examples 1-12, and areference sample. Each binder was prepared according to the followingprocedure:

Molasses (70 g), powdered anhydrous citric acid (20 g), and SOKALAN(BASF) (10 g) were combined in a 1-L beaker. Soft water was then addedto achieve a volume of 450 mL and the resulting mixture was stirred toachieve complete dissolution of solids. To this solution, sodiumhypophosphite (7.5 g) and a silane (Fluorochem, ISI 0200) (0.3 g) wasadded with sufficient water to bring the total volume to 500 mL. Thesolution was stirred for several minutes before being used as describedherein for shell-bone testing. The composition and shell bonelongitudinal tensile strength test result averages for of weathered anddry samples (MN/m²) for comparative example 1-4 and examples 1-10 areshown in Table 1. Column A is the molasses component, column B is themonomeric polycarboxylic acid component, column C is the polymericpolyacrylic acid component and column D is the catalyst. The values incolumn A-C are weight ratio based on total binder weight (i.e.A/[A+B+C]). The values in column D are the weight ratio of catalyst tobinder (D/[A+B+C]).

Referring again to FIG. 1, the reference composition is comprised of amelanoidin-type binder composition which has gained acceptance as acommercially viable binder for a wide range of insulation products. Thecomposition of this sample matches that disclosed in U.S. PublishedApplication No. 2005/0027283. Because the reference composition isregarded as a commercially successful product, it was used as a baselinefrom which to compare the performance characteristics of the exemplarycompositions 1-10. It is well-known to those of ordinary skill in theart that suitable performance in shell-bone testing is highlycorrelative to suitable performance in binding any number of types ofloosely assembled or non-assembled matter, specifically cellulosic andmineral fibers.

Test results are shown in Table 1 which results are mean dry tensilestrength (MN/m²) and mean weathered tensile strength (MN/m²).

TABLE 1 The composition and shell bone longitudinal tensile strengthtest result averages for of weathered and dry samples (MN/m²) forcomparative example 1-4 and examples 1-10. Column A is the molassescomponent, column B is the monomeric polycarboxylic acid component,column C is the polymeric polyacrylic acid component and column D is thecatalyst. The values in column A-C are weight ratio based on totalbinder weight (i.e. A/[A + B + C]). The values in column D are theweight ratio of catalyst to binder (D/[A + B + C]). A B C D DryWeathered Loss/% Comparative 0.6 0.4 0 0.075 1.744 0.528 69.73 Example 1Comparative 0.5 0.5 0 0.075 1.386 0.654 52.84 Example 2 Example 1 0.70.2 0.1 0.05 2.612 1.483 43.21 Example 2 0.8 0.1 0.1 0.05 2.239 1.4933.45 Example 3 0.6 0.2 0.2 0.05 2.591 1.731 33.21 Example 4 0.6 0.2 0.20.025 3.181 1.574 50.5 Comparative 0.6 0.4 0 0.05 1.754 1.086 38.12Example 3 Comparative 0.4 0.6 0 0.05 1.213 0.615 49.29 Example 4 Example5 0.4 0 0.6 0.05 3.53 1.832 48.11 Example 6 0.4 0.3 0.3 0.05 1.918 1.59316.96 Example 7 0.6 0.35 0.033 0.075 1.493 0.786 47.39 Example 8 0.6 0.30.067 0.075 1.644 0.978 40.48 Example 9 0.6 0.2 0.134 0.075 2.432 1.59834.29 Example 10 0.5 0.4 0.067 0.075 1.611 0.913 43.29 Reference 2.3411.518 35.17 Composition

1.-16. (canceled) 17-22. (canceled)
 23. A method of binding loosely ornon-assembled matter comprising: providing an aqueous binder comprisingcarbohydrates having a dextrose equivalent of about 5 to about 100, amonomeric polycarboxylic acid, and a polymeric polycarboxylic acid;disposing the aqueous binder on a collection of matter; and drying theaqueous binder to form an uncured binder and thermally curing theuncured binder to form the collection of matter bound with a cured,thermoset binder.
 24. The method of claim 23, wherein the carbohydratescomprise dextrins.
 25. The method of claim 23, wherein the carbohydratescomprise low molecular-weight carbohydrates.
 26. The method of claim 23,wherein the carbohydrates comprise a sugar selected from the groupconsisting of sucrose, dextrose, fructose and mixtures thereof.
 27. Themethod of claim 23, wherein the polymeric polycarboxylic acid isselected from a group consisting of a polyacrylic acid, polymethacrylicacid, polymaleic acid, copolymers thereof, and mixtures thereof.
 28. Themethod of claim 27, wherein the polymeric polycarboxylic acid has amolecular weight of about 2000 g/mol to about 6000 g/mol.
 29. The methodof claim 23, wherein the monomeric polycarboxylic acid is selected froma group consisting of citric acid, maleic acid, tartaric acid, malicacid, succinic acid, and mixtures thereof.
 30. The method of claim 23,wherein the aqueous binder further comprises a catalyst selected from agroup consisting of an alkali metal polyphosphate, an alkali metaldihydrogen phosphate, a polyphosphoric acid, an alkyl phosphinic acid,and an oligomer or a polymer bearing phosphorous-containing groups andmixtures thereof.
 31. The method of claim 30, wherein the catalyst issodium hypophosphite.
 32. The method of claim 23, wherein the collectionof matter comprises mineral fibers selected from a group consisting ofglass fibers and rock wool fibers.
 33. The method of claim 23, whereinthe cured binder includes between about 0.02% and about 2% nitrogen asdetermined by elemental analysis.
 34. The method of claim 23, in whichthe cured, thermoset binder is formaldehyde free.
 35. The method ofclaim 23, wherein the aqueous binder is disposed on the collection ofmatter by spraying.
 36. The method of claim 23, wherein the collectionof matter is a mineral wool insulation product.
 37. The method of claim23, wherein the aqueous binder further comprises a material selectedfrom the group consisting of a silicon-containing compound,gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane,aminoethylaminopropyltrimethoxysilane, an amino-substituted silane andmixtures thereof.
 38. The method of claim 23, wherein the curingincludes heating at a temperature from about 150° C. to about 315° C.39. The method of claim 23, wherein the cured, thermoset binder is acomposite melanoidin polyester binder.
 40. The method of claim 23,wherein the aqueous binder comprises no more than 50% by dry weight ofthe uncured binder of a combination of the polymeric polycarboxylic acidand the monomeric polycarboxylic acid.
 41. The method of claim 23,wherein in the aqueous binder the ratio of the polymeric polycarboxylicacid to the monomeric polycarboxylic acid is from about 0.25 to about1.5 by weight.
 42. The method of claim 23, wherein in the aqueous binderthe ratio of the carbohydrates to the combination of the carbohydrates,the polymeric polycarboxylic acid, and the monomeric polycarboxylic acidis from about 0.5 to about 0.9 by weight.
 43. The method of claim 23,wherein in the aqueous binder the ratio of the carbohydrates to thecombination of the carbohydrates, the polymeric polycarboxylic acid, andthe monomeric polycarboxylic acid is from about 0.4 to about 0.8 byweight.
 44. The method of claim 23, wherein in the aqueous binder theratio of the carbohydrates to the combination of the carbohydrates, thepolymeric polycarboxylic acid, and the monomeric polycarboxylic acid is0.4 or more by weight.
 45. The method of claim 23, wherein in theaqueous binder the ratio of the carbohydrates to the combination of thecarbohydrates, the polymeric polycarboxylic acid, and the monomericpolycarboxylic acid is 0.9 or less by weight.
 46. The method of claim23, wherein in the aqueous binder the ratio of the polymericpolycarboxylic acid to the combination of the carbohydrates, thepolymeric polycarboxylic acid, and the monomeric polycarboxylic acid isfrom about 0.01 to about 0.4 by weight.
 47. The method of claim 23,wherein in the aqueous binder the ratio of the polymeric polycarboxylicacid to the combination of the carbohydrates, the polymericpolycarboxylic acid, and the monomeric polycarboxylic acid is from about0.033 to about 0.6 by weight.
 48. The method of claim 23, wherein in theaqueous binder the ratio of the polymeric polycarboxylic acid to thecombination of the carbohydrates, the polymeric polycarboxylic acid, andthe monomeric polycarboxylic acid is 0.01 or more by weight.
 49. Themethod of claim 23, wherein in the aqueous binder the ratio of thepolymeric polycarboxylic acid to the combination of the carbohydrates,the polymeric polycarboxylic acid, and the monomeric polycarboxylic acidis 0.6 or less by weight.
 50. The method of claim 23, wherein in theaqueous binder the ratio of the monomeric polycarboxylic acid to thecombination of the carbohydrates, the polymeric polycarboxylic acid, andthe monomeric polycarboxylic acid is from about 0.05 to about 0.4 byweight.
 51. The method of claim 23, wherein in the aqueous binder theratio of the monomeric polycarboxylic acid to the combination of thecarbohydrates, the polymeric polycarboxylic acid, and the monomericpolycarboxylic acid is 0.05 or more by weight.
 52. The method of claim23, wherein in the aqueous binder the ratio of the monomericpolycarboxylic acid to the combination of the carbohydrates, thepolymeric polycarboxylic acid, and the monomeric polycarboxylic acid is0.4 or less by weight.